EP0718378B1 - Non-brilliant coloured pigments - Google Patents

Non-brilliant coloured pigments Download PDF

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Publication number
EP0718378B1
EP0718378B1 EP95119465A EP95119465A EP0718378B1 EP 0718378 B1 EP0718378 B1 EP 0718378B1 EP 95119465 A EP95119465 A EP 95119465A EP 95119465 A EP95119465 A EP 95119465A EP 0718378 B1 EP0718378 B1 EP 0718378B1
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European Patent Office
Prior art keywords
colour pigments
pigments according
pigments
iron oxide
temperatures
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EP95119465A
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German (de)
French (fr)
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EP0718378A2 (en
EP0718378A3 (en
Inventor
Christoph Dr. Schmidt
Claudia Seibel
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Merck Patent GmbH
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Merck Patent GmbH
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/22—Compounds of iron
    • C09C1/24—Oxides of iron
    • C—CHEMISTRY; METALLURGY
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    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/405—Compounds of aluminium containing combined silica, e.g. mica
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A61K8/0254—Platelets; Flakes
    • A61K8/0258—Layered structure
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • C—CHEMISTRY; METALLURGY
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    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C09C1/0021—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a core coated with only one layer having a high or low refractive index
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/06—Treatment with inorganic compounds
    • C09C3/063—Coating
    • C—CHEMISTRY; METALLURGY
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/12—Treatment with organosilicon compounds
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/69—Particle size larger than 1000 nm
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/42—Colour properties
    • A61K2800/43—Pigments; Dyes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/61—Surface treated
    • A61K2800/62—Coated
    • A61K2800/621—Coated by inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10—Interference pigments characterized by the core material
    • C09C2200/102—Interference pigments characterized by the core material the core consisting of glass or silicate material like mica or clays, e.g. kaolin
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    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
    • C09C2200/302—Thickness of a layer with high refractive material
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    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
    • C09C2200/306—Thickness of an absorbing layer
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    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/40—Interference pigments comprising an outermost surface coating
    • C09C2200/401—Inorganic protective coating
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    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/40—Interference pigments comprising an outermost surface coating
    • C09C2200/402—Organic protective coating
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    • C09C2220/00—Methods of preparing the interference pigments
    • C09C2220/10—Wet methods, e.g. co-precipitation

Definitions

  • the present invention relates to non-glossy iron oxide-containing color pigments based on dry ground inorganic platelet-shaped carriers with a particle size of ⁇ 25 ⁇ m, which are characterized in that the iron oxide coating is yellow FeO (OH) and / or Fe 2 O 3 .
  • Classic absorption pigments e.g. Iron oxides usually exist from very small particles with an average particle size of typically 0.1-1 ⁇ m, the specific wavelengths or wavelength ranges of the incident Absorb light and the remaining light essentially diffuse reflect and thus create the complementary color of the absorbed light.
  • Pigments of this type generally have a rough, irregular shape Surface and are more or less opaque.
  • the optical properties are influenced by the average size of the pigment particles, whereby the color purity and depth increases with decreasing average particle size.
  • Pigment particles with a particularly favorable properties average diameter of less than 1 ⁇ m.
  • Such ultrafine pigment particles are generally characterized by poor dispersibility which increases with decreasing particle size.
  • iron oxide pigments in particular are of great economic importance, above all because of their weather resistance, light fastness and the wide range of colors, which range from yellow to red and brown to black.
  • Colored platelet-shaped pigments containing iron oxide are widely described in the literature.
  • Fe 2 O 3 layers optionally with other metal oxides, such as TiO 2 , are applied to a platelet-shaped inorganic carrier, such as mica.
  • a platelet-shaped inorganic carrier such as mica.
  • Such pigments are known from DE 23 13 331.
  • Transparent pigments containing iron oxide are described, which are obtained by coating FeO (OH) or Fe 2 O 3 on mica.
  • Pigments containing iron oxide based on platelet-shaped substrates due to the smooth surface and larger particle diameter, typically 15-100 ⁇ m, others optical properties as absorption pigments.
  • Pearlescent pigments are characterized by a high gloss and low opacity - Properties based on the transparent or semi-transparent substrate material must be returned. For many applications, however, are well-covering Color pigments without gloss needed, e.g. in cosmetic formulations like powder.
  • non-glossy pigments containing iron oxide with a high color strength are obtained if dry-ground inorganic platelet-shaped carriers with a particle size of ⁇ 25 ⁇ m are coated with yellow FeO (OH) and / or Fe 2 O 3 .
  • the color pigments according to the invention show very significant differences in terms of color strength, shade, gloss and hiding power compared to the pearlescent pigments containing iron oxide. This clearly shows that not only the chemical composition of the coating is responsible for the properties of the pigment, but that a whole series of other factors play a role, in particular the structure and the nature of the base substrate as well as the coating process.
  • a lackluster base substrate with an irregular particle shape in combination with FeO (OH) or Fe 2 O 3 coatings on the substrate surface color pigments are obtained which, due to the irregular shape of the surface and the light absorption, only show one color and have no gloss .
  • the invention therefore relates to non-glossy iron oxide-containing color pigments based on dry-ground inorganic platelet-shaped carriers with a particle size of ⁇ 25 ⁇ m, characterized in that dull base substrates with an irregular particle shape are coated with yellow FeO (OH) and / or Fe 2 O 3 .
  • the invention further relates to a method for producing the invention Pigments, which is characterized in that one aqueous suspension of dry milled inorganic platelet Carrier submitted, at temperatures of 5-40 ° C and a pH from 6-9 an aqueous iron (II) salt solution is added with stirring and through the Reaction solution conducts air and / or pure oxygen, then the coated Separates pigment, washes, dries and optionally Temperatures of 400-1000 ° C glows.
  • aqueous suspension of dry milled inorganic platelet Carrier submitted, at temperatures of 5-40 ° C and a pH from 6-9 an aqueous iron (II) salt solution is added with stirring and through the Reaction solution conducts air and / or pure oxygen, then the coated Separates pigment, washes, dries and optionally Temperatures of 400-1000 ° C glows.
  • the basic substrate is an essential component of the color pigment according to the invention.
  • All layered silicates come as a platelet-shaped inorganic carrier, such as. Mica, talc, kaolin or sericite, but also synthetic Mica in question. Mica, e.g. Muscovite or phlogopite, used.
  • Starting materials used in substrates are known and can be by dry grinding the platelet-shaped substrates and subsequent Classify in the desired order.
  • the Layered silicates dry ground have their original platelet shape largely lost. So you get, for example, in the dry Grinding of muscovite mica in a ball mill a white dull Powder, which consists essentially of irregularly shaped particles without Platelet structure exists.
  • the method according to the invention is simple and easy to use.
  • the coating is carried out wet-chemically, the dry-ground layered silicates first being suspended in water.
  • an iron (II) salt such as ammonium iron (II) sulfate, iron (II) halide or in particular iron (II) sulfate, is added at temperatures in the range from 5 to 40 ° C., preferably 10-30 ° C, the pH of the reaction mixture being kept in a range which effects the metal salt hydrolysis. Most conveniently, this is done by simultaneously adding a base such as NaOH, KOH, Na 2 CO 3 or ammonia. However, it is also possible to use a suitable buffer system.
  • the pH should preferably be above 6, especially 6-9.
  • the ferrous salt preferably as aqueous iron (II) salt solution
  • aqueous iron (II) salt solution is used as an oxidizing agent air and / or pure Oxygen passed through the reaction solution, the iron oxide as Iron oxide hydrate precipitates on the substrate in such a way that there are none Incidental precipitation occurs in the suspension.
  • the finished color pigment is finally separated from the reaction mixture, washed with water and generally dried at temperatures of 80-120 ° C.
  • a yellow pigment is obtained which, when dewatered at temperatures of 400-1000 ° C., turns orange due to the conversion of the FeO (OH) into the Fe 2 O 3 .
  • this layer containing iron oxide can have thicknesses of up to approximately 300 nm, preferably 10-80 nm.
  • the color pigments according to the invention can contain up to about 80% by weight, preferably up to 50% by weight, of FeO (OH) or Fe 2 O 3 .
  • all known substrates - both platelet-shaped and non-platelet-shaped substrates with a particle size of 1-25 ⁇ m - can be coated with a FeO (OH) or Fe 2 O 3 layer.
  • Suitable substrates for the process are, in particular, layered silicates, such as talc, kaolin, sericite or mica, platelet-shaped bismuth oxychloride, barium sulfate, synthetic mica, metallic effect pigments, such as platelet-shaped iron oxide, aluminum platelets, for example standard from Eckert, effect pigments, for example from Paliochrom® from BASF, as well as pearlescent pigments - mica flake pigments coated with metal oxides from E. Merck, Darmstadt under the trade name Iriodin.
  • the color pigments according to the invention are provided with an additional top layer.
  • layers of colorless oxides in a known manner, such as TiO 2 , ZrO 2 , Al 2 O 3 , SbO 2 , ZnO, SiO 2 , MgO, CaO, Ce 2 O 3 or SnO 2 , each alone or as Mixture can be applied.
  • a silane or surface-active auxiliaries such as, for example, magnesium stearate.
  • Such a top layer can be applied to pigments that have already dried by the customary methods or even more simply before the pigments are separated from the precipitation solution. In general, the top layer is thinner than the iron oxide or iron oxide hydrate layer.
  • the lackluster color pigments according to the invention are distinguished on the one hand through a high color intensity and a high opacity and on the other due to an extremely high reproducibility of the color tone, which at conventional absorption pigments is often not the case. Besides they show interesting colors in application systems. Furthermore, they are characterized by a very good skin feeling and beneficial Oil absorption values. Because of these properties, the Pigments particularly suitable for aqueous and non-aqueous cosmetic Formulations, but also for cosmetic solid preparations, e.g. Powder, ointments, emulsions, fat sticks and other agents can be used in Concentrations of generally 0.01 to 100 wt.% Are used.
  • the Color pigments also have good dispersibility and redispersibility and are therefore preferably in aqueous or non-aqueous Coating systems from the areas of lacquers, paints and printing inks used.
  • the pigments of the invention are also suitable for Pigmentation of plastics.
  • the invention thus also relates to formulations comprising the formulations according to the invention Color pigments included.
  • Plastics containing the pigments according to the invention are also suitable for laser marking.
  • the color pigments in Concentrations of 0.01 to 20% by weight, preferably 0.5 to 15% by weight, in particular 0.8 to 5% by weight, based on the plastic system the laser markings with high contrast and sharp edges, the are smudge and scratch resistant.
  • the use of this pigmented Plastic can be made in all areas where previously common printing processes are used to label plastics,
  • Example 1 The product from Example 1 is annealed at 850 ° C for 0.5 h. You get one Orange pigment with high color purity.
  • Example 1 The dry ground mica used in Example 1 is made platelet-shaped Mica of particle size ⁇ 15 ⁇ m replaced.
  • the coating with FeO (OH) is carried out analogously to Example 1.
  • the product from comparative example 1 is annealed at 850 ° C. for 0.5 h.
  • the yellow and orange pigments obtained from the examples and the comparative examples are incorporated into a lacquer base (nitrocellulose lacquer) and spread on sheet metal plates.
  • the table shows that those obtained from Examples 1 and 2 Products based on dry ground mica an essential show less gloss than pigments based on platelet-shaped Mica.

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  • Chemical & Material Sciences (AREA)
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  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Wood Science & Technology (AREA)
  • Epidemiology (AREA)
  • Birds (AREA)
  • Nanotechnology (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Cosmetics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Compounds Of Iron (AREA)

Description

Die vorliegende Erfindung betrifft nicht glänzende eisenoxidhaltige Farbpigmente auf Basis von trocken gemahlenen anorganischen plättchenförmigen Trägern der Teilchengröße < 25 µm, die sich dadurch auszeichnen, daß es sich bei der Eisenoxidbeschichtung um gelbes FeO(OH) und/oder Fe2O3 handelt.The present invention relates to non-glossy iron oxide-containing color pigments based on dry ground inorganic platelet-shaped carriers with a particle size of <25 μm, which are characterized in that the iron oxide coating is yellow FeO (OH) and / or Fe 2 O 3 .

Klassische Absorptionspigmente, wie z.B. Eisenoxide, bestehen üblicherweise aus sehr kleinen Partikeln mit einer mittleren Teilchengröße von typischerweise 0,1-1 µm, die bestimmte Wellenlängen bzw. Wellenlängenbereiche des einfallendes Lichtes absorbieren und das restliche Licht im wesentlichen diffus reflektieren und somit die Komplementärfarbe des absorbierten Lichtes erzeugen. Derartige Pigmente weisen im allgemeinen eine rauhe, unregelmäßige Oberfläche auf und sind mehr oder weniger stark opak. Die optischen Eigenschaften werden durch die mittlere Größe der Pigmentpartikel beeinflußt, wobei die Farbreinheit und Farbtiefe mit abnehmender mittlerer Partikelgröße zunimmt. Besonders günstige Eigenschaften weisen Pigmentpartikel mit einem mittleren Durchmesser von weniger als 1 µm auf. Derartige ultrafeine Pigmentpartikel zeichnen sich aber im allgemeinen durch eine schlechte Dispergierbarkeit aus, welche mit abnehmender Partikelgröße zunimmt.Classic absorption pigments, e.g. Iron oxides usually exist from very small particles with an average particle size of typically 0.1-1 µm, the specific wavelengths or wavelength ranges of the incident Absorb light and the remaining light essentially diffuse reflect and thus create the complementary color of the absorbed light. Pigments of this type generally have a rough, irregular shape Surface and are more or less opaque. The optical properties are influenced by the average size of the pigment particles, whereby the color purity and depth increases with decreasing average particle size. Pigment particles with a particularly favorable properties average diameter of less than 1 µm. Such ultrafine pigment particles are generally characterized by poor dispersibility which increases with decreasing particle size.

Bei den Absorptionspigmenten haben insbesondere Eisenoxidpigmente eine große wirtschaftliche Bedeutung, vor allem aufgrund ihrer Wetterbeständigkeit, Lichtechtheit und der breiten Farbskala, die von Gelb über Rot und Braun bis Schwarz reicht. Farbige eisenoxidhaltige plättchenförmige Pigmente, werden in der Literatur vielfach beschrieben. Insbesondere werden dabei Fe2O3-Schichten, gegebenenfalls mit anderen Metalloxiden, wie z.B. TiO2, auf einen plättchenförmigen anorganischen Träger, wie z.B. Glimmer aufgebracht. Derartige Pigmente sind aus der DE 23 13 331 bekannt. In der DE 41 37 764 werden Eisenoxidpigmente auf Basis von SiO2, TiO2 oder ZrO2-Plättchen beansprucht. In Cosmetics & Toiletries, Vol. 107, No. 4, S. 53 ff. werden transparente eisenoxidhaltige Pigmente beschrieben, die durch Beschichtung von FeO(OH) oder Fe2O3 auf Glimmer erhalten werden. In the case of absorption pigments, iron oxide pigments in particular are of great economic importance, above all because of their weather resistance, light fastness and the wide range of colors, which range from yellow to red and brown to black. Colored platelet-shaped pigments containing iron oxide are widely described in the literature. In particular, Fe 2 O 3 layers, optionally with other metal oxides, such as TiO 2 , are applied to a platelet-shaped inorganic carrier, such as mica. Such pigments are known from DE 23 13 331. DE 41 37 764 claims iron oxide pigments based on SiO 2 , TiO 2 or ZrO 2 platelets. In Cosmetics & Toiletries, Vol. 107, No. 4, p. 53 ff., Transparent pigments containing iron oxide are described, which are obtained by coating FeO (OH) or Fe 2 O 3 on mica.

Eisenoxidhaltige Pigmente auf Basis plättchenförmiger Substrate, die sogenannten Perlglanzpigmente, weisen aufgrund der glatten Oberfläche und des größeren Partikeldurchmessers, typischerweise bei 15-100 µm, andere optische Eigenschaften auf als Absorptionspigmente. Perlglanzpigmente zeichnen sich durch einen hohen Glanz und ein geringes Deckvermögen aus - Eigenschaften, die auf das transparente oder semitransparente Substratmaterial zurückgeführt werden müssen. Für viele Anwendungen werden aber gut-deckende Farbpigmente ohne Glanz benötigt, z.B. in kosmetischen Formulierungen wie Pudern.Pigments containing iron oxide based on platelet-shaped substrates, the so-called Pearlescent pigments, due to the smooth surface and larger particle diameter, typically 15-100 µm, others optical properties as absorption pigments. Pearlescent pigments are characterized by a high gloss and low opacity - Properties based on the transparent or semi-transparent substrate material must be returned. For many applications, however, are well-covering Color pigments without gloss needed, e.g. in cosmetic formulations like powder.

Es bestand daher die Aufgabe glanzlose Farbpigmente zu finden, die neben der Körperfarbe ein hohes Deckvermögen aufweisen, gut dispergierbar sind und keinen der oben genannten Nachteile aufweisen.It was therefore the task of finding dull color pigments that besides the body color has a high hiding power, is well dispersible and have none of the disadvantages mentioned above.

Überraschenderweise wurde nun gefunden, daß man nicht glänzende eisenoxidhaltige Pigmente mit hoher Farbstärke erhält, wenn man trocken gemahlene anorganische plättchenförmige Träger der Teilchengröße < 25 µm mit gelbem FeO(OH) und/oder Fe2O3 beschichtet.Surprisingly, it has now been found that non-glossy pigments containing iron oxide with a high color strength are obtained if dry-ground inorganic platelet-shaped carriers with a particle size of <25 μm are coated with yellow FeO (OH) and / or Fe 2 O 3 .

Aus der EP 0 659 843 A1, einem Stand der Technik nach A 54(3), (4) EPÜ, sind Eisenoxidpigmente auf Basis eines unregelmäßig geformten Glimmerteilchens bekannt. Das dort beschriebene Pigment wird nach einem Verfahren hergestellt das zu roten Eisenoxidpigmenten führt.From EP 0 659 843 A1, a prior art according to A 54 (3), (4) EPC, are iron oxide pigments based on an irregular shape Mica particle known. The pigment described there becomes a process that produces red iron oxide pigments leads.

Die erfindungsgemäßen Farbpigmente zeigen in Bezug auf Farbstärke, Farbnuancierung, Glanz und Deckvermögen ganz wesentliche Unterschiede im Vergleich zu den eisenoxidhaltigen Perlglanzpigmenten. Das zeigt eindeutig, daß nicht allein die chemische Zusammensetzung der Beschichtung für die Eigenschaften des Pigments verantwortlich sind, sondern, daß eine ganze Reihe weiterer Faktoren eine Rolle spielen, insbesondere der Aufbau und die Beschaffenheit des Basissubstrats als auch das Beschichtungsverfahren. Durch die Verwendung eines glanzlosen Basissubstrats mit unregelmäßiger Teilchenform in Kombination mit FeO(OH)- bzw. Fe2O3-Belegungen auf der Substratoberfläche erhält man Farbpigmente, die aufgrund der irregulären Form der Oberfläche und der Lichtabsorption nur eine Farbe zeigen und keinen Glanz besitzen. The color pigments according to the invention show very significant differences in terms of color strength, shade, gloss and hiding power compared to the pearlescent pigments containing iron oxide. This clearly shows that not only the chemical composition of the coating is responsible for the properties of the pigment, but that a whole series of other factors play a role, in particular the structure and the nature of the base substrate as well as the coating process. By using a lackluster base substrate with an irregular particle shape in combination with FeO (OH) or Fe 2 O 3 coatings on the substrate surface, color pigments are obtained which, due to the irregular shape of the surface and the light absorption, only show one color and have no gloss .

Gegenstand der Erfindung sind daher nicht glänzende eisenoxidhaltige Farbpigmente auf Basis von trocken gemahlenen anorganischen plättchenförmigen Trägern der Teilchengröße < 25 µm, dadurch gekennzeichnet, daß glanzlose Basissubstrate mit unregelmäßiger Teilchenform mit gelbem FeO(OH) und/oder Fe2O3 beschichtet werden. The invention therefore relates to non-glossy iron oxide-containing color pigments based on dry-ground inorganic platelet-shaped carriers with a particle size of <25 µm, characterized in that dull base substrates with an irregular particle shape are coated with yellow FeO (OH) and / or Fe 2 O 3 .

Gegenstand der Erfindung ist weiterhin ein Verfahren zur Herstellung der erfindungsgemäßen Pigmente, das sich dadurch auszeichnet, daß man eine wäßrige Suspension des trocken gemahlenen anorganischen plättchenförmigen Trägers vorlegt, bei Temperaturen von 5-40 °C und einem pH-Wert von 6-9 eine wäßrige Eisen(II)salzlösung unter Rühren zugesetzt und durch die Reaktionslösung Luft und/oder reinen Sauerstoff leitet, danach das beschichtete Pigment abtrennt, wäscht, trocknet und gegebenenfalls bei Temperaturen von 400-1000 °C glüht.The invention further relates to a method for producing the invention Pigments, which is characterized in that one aqueous suspension of dry milled inorganic platelet Carrier submitted, at temperatures of 5-40 ° C and a pH from 6-9 an aqueous iron (II) salt solution is added with stirring and through the Reaction solution conducts air and / or pure oxygen, then the coated Separates pigment, washes, dries and optionally Temperatures of 400-1000 ° C glows.

Wesentlicher Bestandteil des erfindungsgemäßen Farbpigments ist das Basissubstrat. Als plättchenförmiger anorganischer Träger kommen alle Schichtsilikate, wie z.B. Glimmer, Talk, Kaolin oder Sericit, aber auch synthetischer Glimmer in Frage. Bevorzugt wird Glimmer, wie z.B. Muskovit oder Phlogopit, eingesetzt. In der Regel werden Substrate mit einer Teilchengröße < 25 µm, und insbesondere < 15 µm, eingesetzt. Die als Substrate verwendeten Ausgangsmaterialien sind bekannt und lassen sich durch trockenes Vermahlen der plättchenförmigen Substrate und nachfolgendes Klassieren in der gewünschten Größenordnung gewinnen. Die trocken gemahlenen Schichtsilikate haben ihre ursprüngliche Plättchenform weitestgehend verloren. So erhält man beispielsweise bei der trockenen Mahlung von Muskovit-Glimmer in einer Kugelmühle ein weißes glanzloses Pulver, welches im wesentlichen aus unregelmäßig geformten Partikeln ohne Plättchenstruktur besteht.The basic substrate is an essential component of the color pigment according to the invention. All layered silicates come as a platelet-shaped inorganic carrier, such as. Mica, talc, kaolin or sericite, but also synthetic Mica in question. Mica, e.g. Muscovite or phlogopite, used. As a rule, substrates with a particle size <25 µm, and in particular <15 µm, used. As Starting materials used in substrates are known and can be by dry grinding the platelet-shaped substrates and subsequent Classify in the desired order. The Layered silicates dry ground have their original platelet shape largely lost. So you get, for example, in the dry Grinding of muscovite mica in a ball mill a white dull Powder, which consists essentially of irregularly shaped particles without Platelet structure exists.

Das erfindungsgemäße Verfahren ist einfach und leicht zu handhaben. Die Beschichtung erfolgt naßchemisch, wobei zunächst die trocken gemahlenen Schichtsilikate in Wasser suspendiert werden. Anschließend erfolgt die Zugabe eines Eisen(II)salzes, wie z.B. Ammonium-Eisen(II)sulfat, Eisen(II)halogenid oder insbesondere Eisen(II)sulfat, bei Temperaturen im Bereich von 5 bis 40 °C, vorzugsweise 10-30 °C, wobei der pH-Wert des Reaktionsgemisches in einem Bereich gehalten wird, der die Metallsalzhydrolyse bewirkt. Am zweckmäßigsten geschieht dies durch gleichzeitige Zugabe einer Base, wie z.B. NaOH, KOH, Na2CO3 oder Ammoniak. Es ist jedoch auch möglich ein geeignetes Puffersystem zu verwenden. Der pH-Wert sollte vorzugsweise oberhalb von 6 liegen, insbesondere bei 6-9. The method according to the invention is simple and easy to use. The coating is carried out wet-chemically, the dry-ground layered silicates first being suspended in water. Subsequently, an iron (II) salt, such as ammonium iron (II) sulfate, iron (II) halide or in particular iron (II) sulfate, is added at temperatures in the range from 5 to 40 ° C., preferably 10-30 ° C, the pH of the reaction mixture being kept in a range which effects the metal salt hydrolysis. Most conveniently, this is done by simultaneously adding a base such as NaOH, KOH, Na 2 CO 3 or ammonia. However, it is also possible to use a suitable buffer system. The pH should preferably be above 6, especially 6-9.

Während und/oder nach der Zugabe des Eisen(II)salzes, vorzugsweise als wäßrige Eisen(II)salz-Lösung, wird als Oxidationsmittel Luft und/oder reiner Sauerstoff durch die Reaktionslösung geleitet, wobei sich das Eisenoxid als Eisenoxidhydrat auf dem Substrat derart niederschlägt, daß es zu keinen Nebenfällungen in der Suspension kommt.During and / or after the addition of the ferrous salt, preferably as aqueous iron (II) salt solution, is used as an oxidizing agent air and / or pure Oxygen passed through the reaction solution, the iron oxide as Iron oxide hydrate precipitates on the substrate in such a way that there are none Incidental precipitation occurs in the suspension.

Das fertige Farbpigment wird zuletzt aus dem Reaktionsgemisch abgetrennt, mit Wasser gewaschen und in der Regel bei Temperaturen von 80-120 °C getrocknet. Man erhält ein Gelbpigment, das sich beim Entwässern bei Temperaturen von 400-1000 °C orange verfärbt aufgrund der Umwandlung des FeO(OH) in das Fe2O3.The finished color pigment is finally separated from the reaction mixture, washed with water and generally dried at temperatures of 80-120 ° C. A yellow pigment is obtained which, when dewatered at temperatures of 400-1000 ° C., turns orange due to the conversion of the FeO (OH) into the Fe 2 O 3 .

Diese eisenoxidhaltige Schicht kann je nach gewünschter Farbstärke Dicken bis zu etwa 300 nm, vorzugsweise 10-80 nm aufweisen. Die erfindungsgemäßen Farbpigmente können bis etwa 80 Gew.%, vorzugsweise bis 50 Gew.%, an FeO(OH) bzw. Fe2O3 enthalten.Depending on the desired color strength, this layer containing iron oxide can have thicknesses of up to approximately 300 nm, preferably 10-80 nm. The color pigments according to the invention can contain up to about 80% by weight, preferably up to 50% by weight, of FeO (OH) or Fe 2 O 3 .

Nach dem erfindungsgemäßen Verfahren können alle bekannten Substrate - sowohl plättchenförmige als auch nicht plättchenförmige Substrate mit einer Teilchengröße von 1-25 µm mit einer FeO(OH) oder Fe2O3-Schicht beschichtet werden.According to the method of the invention, all known substrates - both platelet-shaped and non-platelet-shaped substrates with a particle size of 1-25 μm - can be coated with a FeO (OH) or Fe 2 O 3 layer.

Geeignete Substrate für das Verfahren sind insbesondere Schichtsilikate, wie z.B. Talk, Kaolin, Sericit oder Glimmer, plättchenförmiges Wismutoxichlorid, Bariumsulfat, synthetischer Glimmer, Metalleffektpigmente, wie plättchenförmiges Eisenoxid, Aluminiumplättchen, z.B. Standard von der Fa. Eckert, Effektpigmente, wie z.B. Paliochrom® von der BASF, sowie Perlglanzpigmente - mit Metalloxiden beschichtete Glimmerschuppenpigmente der Fa. E. Merck, Darmstadt unter dem Handelsnamen Iriodin. Letztere sind z.B. aus den deutschen Patenten und Patentanmeldungen 14 67 468, 19 59 998, 20 09 566, 22 14 545, 22 15 191, 22 44 298, 23 13 331, 25 22 272, 31 37 808, 31 37 809, 31 51 343, 31 51 354, 31 51 355, 32 11 602 und 32 35 017 bekannt. Besonders bevorzugt werden mit TiO2 und/oder Fe2O3 beschichtete Glimmerpigmente sowie unbeschichtete oder mit ein oder mehreren Metalloxiden beschichtete SiO2-Flakes, Glasflakes, Keramikflakes oder synthetische trägerfreie Plättchen eingesetzt. Suitable substrates for the process are, in particular, layered silicates, such as talc, kaolin, sericite or mica, platelet-shaped bismuth oxychloride, barium sulfate, synthetic mica, metallic effect pigments, such as platelet-shaped iron oxide, aluminum platelets, for example standard from Eckert, effect pigments, for example from Paliochrom® from BASF, as well as pearlescent pigments - mica flake pigments coated with metal oxides from E. Merck, Darmstadt under the trade name Iriodin. The latter are, for example, from German patents and patent applications 14 67 468, 19 59 998, 20 09 566, 22 14 545, 22 15 191, 22 44 298, 23 13 331, 25 22 272, 31 37 808, 31 37 809, 31 51 343, 31 51 354, 31 51 355, 32 11 602 and 32 35 017 are known. Mica pigments coated with TiO 2 and / or Fe 2 O 3 and uncoated or coated with one or more metal oxides, SiO 2 flakes, glass flakes, ceramic flakes or synthetic carrier-free platelets are particularly preferably used.

In manchen Fällen ist es zweckmäßig die erfindungsgemäßen Farbpigmente, zusätzlich mit einer Deckschicht zu versehen. Zweckmäßigerweise wird man hierfür in bekannter Weise Schichten farbloser Oxide wählen, wie z.B. TiO2, ZrO2, Al2O3, SbO2, ZnO, SiO2, MgO, CaO, Ce2O3 oder SnO2, die jeweils allein oder als Gemisch aufgebracht werden können. Für die Hydrophobierung der Oberfläche zur Anpassung an bestimmte Anwendungssysteme empfiehlt es sich, die erfindungsgemäßen Farbpigmente mit einem Silan oder oberflächenaktive Hilfsmitteln, wie z.B. Magnesiumstearat, zu behandeln. Eine solche Deckschicht kann nach den üblichen Methoden auf bereits getrocknete Pigmente aufgebracht werden oder auch noch einfacher vor der Abtrennung der Pigmente aus der Fällösung. Im allgemeinen ist die Deckschicht dünner als die Eisenoxid- bzw. Eisenoxidhydrat-Schicht.In some cases it is advisable to provide the color pigments according to the invention with an additional top layer. Appropriately, one will choose layers of colorless oxides in a known manner, such as TiO 2 , ZrO 2 , Al 2 O 3 , SbO 2 , ZnO, SiO 2 , MgO, CaO, Ce 2 O 3 or SnO 2 , each alone or as Mixture can be applied. For the hydrophobization of the surface to adapt to certain application systems, it is advisable to treat the color pigments according to the invention with a silane or surface-active auxiliaries, such as, for example, magnesium stearate. Such a top layer can be applied to pigments that have already dried by the customary methods or even more simply before the pigments are separated from the precipitation solution. In general, the top layer is thinner than the iron oxide or iron oxide hydrate layer.

Die erfindungsgemäßen glanzlosen Farbpigmente zeichnen sich zum einen durch eine hohe Farbintensität und ein hohes Deckvermögen und zum anderen durch eine überaus hohe Reproduzierbarkeit des Farbtons aus, was bei konventionellen Absorptionspigmenten häufig nicht der Fall ist. Daneben zeigen sie interessante Farbtöne in anwendungstechnischen Systemen. Weiterhin zeichnen sie sich durch ein sehr gutes skin-feeling und vorteilhafte Werte für die Ölabsorption aus. Aufgrund dieser Eigenschaften sind die Pigmente insbesondere geeignet für wäßrige und nicht wäßrige kosmetische Formulierungen, aber auch für kosmetische Feststoffzubereitungen, wie z.B. Puder, Salben, Emulsionen, Fettstiften und anderen Mitteln und können in Konzentrationen von in der Regel 0,01 bis 100 Gew.% eingesetzt werden. Die Farbpigmente weisen darüberhinaus eine gute Dispergierbarkeit und Redispergierbarkeit auf und werden daher vorzugsweise in wäßrigen oder nicht wäßrigen Beschichtungssystemen aus den Bereichen Lacke, Farben und Druckfarben verwendet. Weiterhin eignen sich die erfindungsgemäßen Pigmente zur Pigmentierung von Kunststoffen.The lackluster color pigments according to the invention are distinguished on the one hand through a high color intensity and a high opacity and on the other due to an extremely high reproducibility of the color tone, which at conventional absorption pigments is often not the case. Besides they show interesting colors in application systems. Furthermore, they are characterized by a very good skin feeling and beneficial Oil absorption values. Because of these properties, the Pigments particularly suitable for aqueous and non-aqueous cosmetic Formulations, but also for cosmetic solid preparations, e.g. Powder, ointments, emulsions, fat sticks and other agents can be used in Concentrations of generally 0.01 to 100 wt.% Are used. The Color pigments also have good dispersibility and redispersibility and are therefore preferably in aqueous or non-aqueous Coating systems from the areas of lacquers, paints and printing inks used. The pigments of the invention are also suitable for Pigmentation of plastics.

Gegenstand der Erfindung sind somit auch Formulierungen, die die erfindungsgemäßen Farbpigmente enthalten.The invention thus also relates to formulations comprising the formulations according to the invention Color pigments included.

Kunststoffe enthaltend die erfindungsgemäßen Pigmente sind weiterhin geeignet für die Lasermarkierung. Durch den Zusatz der Farbpigmente in Konzentrationen von 0,01 bis 20 Gew.%, vorzugsweise 0,5 bis 15 Gew.%, insbesondere 0,8 bis 5 Gew.%, bezogen auf das Kunststoffsystem werden bei den Lasermarkierungen kontrastreiche und kantenscharfe Markierungen, die wisch- und kratzfest sind, erhalten. Die Verwendung dieses pigmentierten Kunststoffes kann auf allen Gebieten erfolgen, wo bisher übliche Druckverfahren zur Beschriftung von Kunststoffen eingesetzt werden,Plastics containing the pigments according to the invention are also suitable for laser marking. By adding the color pigments in Concentrations of 0.01 to 20% by weight, preferably 0.5 to 15% by weight, in particular 0.8 to 5% by weight, based on the plastic system the laser markings with high contrast and sharp edges, the are smudge and scratch resistant. The use of this pigmented Plastic can be made in all areas where previously common printing processes are used to label plastics,

Die nachfolgenden Beispiele sollen die Erfindung erläutern, ohne sie zu begrenzen:The following examples are intended to illustrate the invention without restricting it limit:

Beispiel 1example 1

100 g trocken gemahlener Glimmer mit einer Teilchengröße von < 12 µm werden in 2 l Wasser suspendiert. Mit 10%iger Salzsäure wird der pH-Wert auf 7,5 eingestellt. Bei 20 °C wird zu dieser Pigmentsuspension eine wäßrige FeSO4-Lösung (120 g FeSO4 · 7 H2O in 420 ml Wasser) zugetropft. Gleichzeitig wird Sauerstoff mit einer Rate von 30 l/min durch die Suspension geleitet. Während der Reaktion wird der pH-Wert mit 10%iger Na2CO3-Lösung auf pH = 7-8 konstant gehalten. Nach beendeter Zugabe der FeSO4-Lösung wird noch 15 Minuten gerührt. Zuletzt wird mit Wasser sulfatfrei gewaschen, das Produkt bei 110 °C getrocknet und auf 100 µm gesiebt. Das fertige Pigment enthält 25,6 Gew.% FeO(OH) und zeichnet sich durch seine intensive gelb-orange Farbe aus.100 g of dry mica with a particle size of <12 µm are suspended in 2 l of water. The pH is adjusted to 7.5 with 10% hydrochloric acid. An aqueous FeSO 4 solution (120 g FeSO 4 .7H 2 O in 420 ml water) is added dropwise to this pigment suspension at 20 ° C. At the same time, oxygen is passed through the suspension at a rate of 30 l / min. During the reaction, the pH is kept constant at pH = 7-8 with 10% Na 2 CO 3 solution. After the addition of the FeSO 4 solution has ended, the mixture is stirred for a further 15 minutes. Finally, the product is washed sulfate-free with water, the product is dried at 110 ° C. and sieved to 100 μm. The finished pigment contains 25.6% by weight FeO (OH) and is characterized by its intense yellow-orange color.

Beispiel 2Example 2

Das Produkt aus Beispiel 1 wird 0,5 h bei 850 °C geglüht. Man erhält ein Orangepigment mit hoher Farbreinheit.The product from Example 1 is annealed at 850 ° C for 0.5 h. You get one Orange pigment with high color purity.

Vergleichsbeispiel 1Comparative Example 1

Der in Beispiel 1 verwendete trocken gemahlene Glimmer wird durch plättchenförmigen Glimmer der Teilchengröße < 15 µm ersetzt. Die Beschichtung mit FeO(OH) erfolgt analog Beispiel 1. The dry ground mica used in Example 1 is made platelet-shaped Mica of particle size <15 µm replaced. The coating with FeO (OH) is carried out analogously to Example 1.

Vergleichsbeispiel 2Comparative Example 2

Das Produkt aus Vergleichsbeispiel 1 wird 0,5 h bei 850 °C geglüht.The product from comparative example 1 is annealed at 850 ° C. for 0.5 h.

Koloristische BewertungColoristic evaluation

Die aus den Beispielen und den Vergleichsbeispielen erhaltenen Gelb- und Orangepigmente werden in eine Lackgrundlage (Nitrocelluloselack) eingearbeitet und auf Blechplatten aufgestrichen. Die Farb- und Glanzcharakteristik wird nach der Lab-Methode (DIN 5033 Hunter-LAB) gemessen. Aus den Helligkeitswerten (L-Werten) der Lackkarten - Meßgeometrien 22,5°/22,5° und 45°/0° - wird nach folgender Formel das reflektierte Licht (Glanz) aus unterschiedlich zurückgelegten Wegen erfaßt: Glanzzahl = L22,5°/22,5° - L45°/0° L22.5°/22,5° x 100 Produkt Glanzzahl Beispiel 1 30,6 Vergleichsbeispiel 1 50,6 Beispiel 2 34,4 Vergleichsbeispiel 2 42,8 The yellow and orange pigments obtained from the examples and the comparative examples are incorporated into a lacquer base (nitrocellulose lacquer) and spread on sheet metal plates. The color and gloss characteristics are measured using the Lab method (DIN 5033 Hunter-LAB). From the brightness values (L values) of the paint cards - measurement geometries 22.5 ° / 22.5 ° and 45 ° / 0 ° - the reflected light (gloss) is recorded from different paths: Gloss number = L 22.5 ° / 22.5 ° - L 45 ° / 0 ° L 22.5 ° / 22.5 ° x 100 product Gloss number example 1 30.6 Comparative Example 1 50.6 Example 2 34.4 Comparative Example 2 42.8

Aus der Tabelle geht hervor, daß die aus den Beispielen 1 und 2 erhaltenen Produkte auf Basis von trocken gemahlenen Glimmer einen wesentlich geringeren Glanz zeigen als Pigmente auf Basis von plättchenförmigen Glimmer.The table shows that those obtained from Examples 1 and 2 Products based on dry ground mica an essential show less gloss than pigments based on platelet-shaped Mica.

Claims (9)

  1. Non-lustrous iron oxide-containing colour pigments based on dry-milled inorganic plateletlike substrates having a particle size of < 25 µm, characterized in that the lustreless basic substrates of irregular particle morphology are coated with yellow FeO(OH) and/or Fe2O3.
  2. Colour pigments according to Claim 1, characterized in that the iron oxide-containing layer consists uniformly of Fe2O3 which has been prepared by dehydrating FeO(OH) at temperatures of 400 - 1000°C.
  3. Colour pigments according to Claim 1 or 2, characterized in that the content of iron oxide or iron hydroxide is from 5 to 70% by weight, based on the overall pigment.
  4. Colour pigments according to one of Claims 1 to 3, characterized in that the inorganic plateletlike substrate is mica.
  5. Colour pigments according to one of Claims 1 to 4, characterized in that they additionally contain a covering layer comprising one or more colourless metal oxides, silane compounds or stearates or combinations of these compounds.
  6. Process for the preparation of colour pigments according to Claim 1, characterized in that an aqueous suspension of the dry-milled inorganic plateletlike substrate is used as initial charge, an aqueous iron(II) salt solution is added at temperatures of 5 - 40°C and at a pH of 6 - 9, and air and/or oxygen is passed through the reaction solution, after which the coated pigment is isolated, washed, dried and, if desired, calcined at temperatures of 400 - 1000°C.
  7. Use of the colour pigments according to Claim 1 in coatings, inks, plastics and in cosmetic formulations.
  8. Formulations comprising colour pigments according to Claim 1.
  9. Laser-markable plastics comprising colour pigments according to Claim 1.
EP95119465A 1994-12-21 1995-12-11 Non-brilliant coloured pigments Expired - Lifetime EP0718378B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4445394 1994-12-21
DE4445394 1994-12-21

Publications (3)

Publication Number Publication Date
EP0718378A2 EP0718378A2 (en) 1996-06-26
EP0718378A3 EP0718378A3 (en) 1996-08-21
EP0718378B1 true EP0718378B1 (en) 2001-11-07

Family

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Application Number Title Priority Date Filing Date
EP95119465A Expired - Lifetime EP0718378B1 (en) 1994-12-21 1995-12-11 Non-brilliant coloured pigments

Country Status (6)

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EP (1) EP0718378B1 (en)
JP (1) JP3713086B2 (en)
KR (1) KR960022862A (en)
CN (1) CN1133324A (en)
DE (2) DE19546058A1 (en)
ES (1) ES2165887T3 (en)

Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN100551979C (en) * 2003-12-17 2009-10-21 Ppg工业俄亥俄公司 Coating composition with enhanced corrosion resistance and outward appearance

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19618569A1 (en) † 1996-05-09 1997-11-13 Merck Patent Gmbh Highly transparent multilayer interference pigments for lacquers, inks, cosmetics, laser-markable plastics etc.
PT978373E (en) * 1998-08-06 2011-11-17 Sicpa Holding Sa Inorganic sheet for making pigments
DE19905415A1 (en) * 1999-02-10 2000-08-17 Hoechst Trespaphan Gmbh Transparent biaxially oriented polyolefin film
JP4786011B2 (en) * 2000-03-29 2011-10-05 株式会社 資生堂 Iron oxide-bismuth compound composite pigment and cosmetic containing the same
DE102006060997A1 (en) * 2006-12-20 2008-06-26 Merck Patent Gmbh pearlescent
JP5413554B2 (en) * 2008-04-25 2014-02-12 戸田工業株式会社 Coloring pigment for sunlight high reflection paint
EP2808363B1 (en) * 2012-01-23 2018-11-21 Topy Kogyo Kabushiki Kaisha Iron oxide-coated layered silicate pigment

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DE2313331C2 (en) * 1973-03-17 1986-11-13 Merck Patent Gmbh, 6100 Darmstadt Mica flake pigments containing iron oxide
JPS5876461A (en) * 1981-10-26 1983-05-09 メルク・パテント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング Transparent coloring pigment and manufacture
DE3375981D1 (en) * 1982-11-10 1988-04-21 Basf Corp Pearlescent automotive paint compositions
US4499143A (en) * 1983-08-26 1985-02-12 Inmont Corporation Multilayer automative paint system
IN165908B (en) * 1985-10-25 1990-02-10 Merck Patent Gmbh
JPS63145410A (en) * 1986-11-29 1988-06-17 Hosokawa Micron Kk Synthetic fiber
DE4209242A1 (en) * 1992-03-21 1993-09-23 Basf Ag MIXTURES SUITABLE AS GLOSS PIGMENTS
EP0659843B1 (en) * 1993-11-25 2002-02-13 MERCK PATENT GmbH Non-brilliant pigment

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100551979C (en) * 2003-12-17 2009-10-21 Ppg工业俄亥俄公司 Coating composition with enhanced corrosion resistance and outward appearance

Also Published As

Publication number Publication date
DE59509808D1 (en) 2001-12-13
KR960022862A (en) 1996-07-18
DE19546058A1 (en) 1996-06-27
ES2165887T3 (en) 2002-04-01
EP0718378A2 (en) 1996-06-26
JPH08231880A (en) 1996-09-10
CN1133324A (en) 1996-10-16
JP3713086B2 (en) 2005-11-02
EP0718378A3 (en) 1996-08-21

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